Treating concrete.



35 rubber resin.

45 crete coatings.

TED STATES PA nnrcE.

, CARIISETON ELLIS, F MONTCLAIR, NEW JERSEY.

TREATING CONCRETE.

No Drawing.

or finishing compositions and more particularly to the process ofcoating concretefto form a new article of manufacture or concreteroduct, all as more fully hereinafte described and as claimed. Thepresent invention rovides a composition capable of withstan mg thedisintegrating action of weather and alkali and which I may be given abody or consistency dependent on the degree of porosity of concrete.

As ordinarily prepared concrete'is a fairlyporous material andabsorbsoil very easily by capillary action. In the parlance of the tradethis action is known as suction and for the preliminary coating ofconcrete, oils of high body which resist suction to a 'consid erabledegree are often required. Various materials are therefore set forth inthe present invention for the pn pose of providing consistenciessuitable forthe various conditions of concrete and cement coating.

As a basis for cementand concrete (gaiting I preferably make use of aresinous base of a substantially unsaponifiable character, such forexample as Jelutong or Pontianak These resins are essentially orcharacteristically unsaponifiable and thus differ from the resinsordinarily used in the making of varnishes and paint mediums. To be surethere is, in-some of the ordinary 40 resins, especially the harder sortsasmall and varying amount of unsaponifiable matter but essentially theresins of the varnish trade are saponifiable bodies and therefore notwell fitted for serving as a basis for con- Most of the resins used inthe making of varnishes and paint oils contain not only saponifiableesters but often a large amount of free resin acids. Boiling alcoholicpotash readily saponifies these constituents but the a'lkalis of cementhave only types of concrete primers, the speed of neu- Specification ofLetters Patent.

Patented July 4t, 191-6.

Application filed October 17, 1911. Serial No. 655,214.

component acts rapidly, neutralization may be effected before the.coating has set "and dried. If the action of the acid component is slow,neutralization and reaction may go on after setting and drying of thecompositlon thus causing rupturing of the coating and its ultimatedestruction. The resin acids differ from the fatty acids in thisrespect. They are slower than the fatty acids in neutralizing activity,so slow in fact that under ordinary conditions a coating can tralizationhas to be considered. If the acid pound has opportunity to" dry andharden before neutralizing reactions are fairly under way and thesesubsequently progress to the detriment of the coating.

The following brief comparison may serve to explain the differencesnoted. The fats are bodies of synthetic origin and as glycerids formwell characterized bodies. The resins are largely bodies resulting fromcondensation, are very fluctuating in composition and the nature oftheir components is not at all Well established at the "present timerThe copals which are so extensively used in varnish making, vary incomposition very greatly. Manila copal, for example, may have an acidnumber of 135 and a sa ponifiable value of 185, while Angola copal willperhaps give an acid number of 60 and a saponifiable value of 135.Borneo 'copal will give an acid number of about 145 and a saponifiablevalue of say 180, Amber-contains about 30% resin acids and nearly 70%Common resin has an acid number of about 140, although this ofsaponifiable esters.

varies considerably with different grades.

about 150 but is also subject to considerable variation in composition.However the uncertain composition of resins makes all these figures ofindifferent value and the variations in ester value and acidity,together with the further changes taking place in the fu sing or meltingof the hard gums or resins, preparatory to mixing with oils and thinners, leaves in doubt, always, the action of the resin acids and esterson the alkali. The use therefore of short .oil varnishes, that isvarnishes high in saponifiable resin and low in oil, for coating cementstructures is at best only a makeshift. The fatty acids from ordinaryfats, including such well defined bodies as stearic, palmitic and oleicacids, are more rapid in theirfineutralizing action and are mprehomogeneous in composition so that their reaction with cement alkali ismore effective and decisive. The

lime soaps of the non-drying oils. The drying oils are better adapted toresist the hydrolyzing action of moisture, as their lime soaps, whenapplied to concrete in the form of a solution in a suitable solvent orwhen 'formedin or on the cement by the action of their fatty acidsapplied as a priming coat, for example, undergo oxidation and formoxidized soaps which do not exhibit the same hydrolyzable tendencies. Ofthe drying oils the acid derived from tung oil is perhaps mostsatisfactory in this respect. The lime tungate which forms on applyingtung acid to concrete has excellent water-proofing qualities. Second inthis respect, ordinarily, are the acids of fish and linseed oils.

In an application entitled Cement primer, filed May 24, 1909, Ser.No.1497,934; application for binding and coating composition, filedMarch 29, 1910, Ser. No. 552,178; application for process of coatingconcrete, filed Oct. 22, 1910, Ser. No. 588,549, now Letters- Patent No.999,493 of Aug. 1, 1911; application for Waterproofing coatingcomposition for concrete, etc., filed Feb. 16, 1911, Ser. No. 608,888,now Letters Patent No.

999,708 of Aug. 1, 1911; application for concrete and stucco paint oil,filed May 20, 1911, Ser. No. 628,577, now Letters Patent No. 1,005,818of Oct. 17, 1911; and application for composition for priming andcoating concrete, filed July 14, 1911, Ser. No. 638,515, now LettersPatent No. 1,006,7 37 of Oct. 24, 1911, I have set forth the use offatty acid neutralizers and unsaponifiable-or substantiallyunsaponifiable resinous or other bodies with or Without colloidalthickeners 'or bodyingmaterials for the priming, or coating of concreteand other structures-' and have set forth in particular the advantagesof J elutong or Pontianak rubber resin for this purpose. The presentapplication contains certaln matter derived from the foregoing LettersPatent and applications.

Jelutong resin is a waste or by-product derived from the deresination ofpontianak, as will be hereinafter set forth more in de tail, and itsresistance to alkali, due to its relatively very high proportion ofunsaponifiable bodies, makes its especially useful an the coating of,concrete. quality apparently resides, as indicated, in the very low oralmost complete absence of the acids and readily saponifiable estersordinarily found in varnish resins of the usual 1 with coal tarnaphth'amay be used more or less; especially if, asset forth in U. S. LettersPatent No. 999,493, the petroleum product is more volatile than thearomatic product. In the foregoing formulas, in case the raw resin isused, the coal tar naphtha may be replaced to the extent of 10%20%, moreor less by petroleum naphtha.

As stated, a colloidal thickener is required for solutions which are tobe applied to very porous concrete, for the rubber resin solution asusually prepared has rather slight body in concentration of 25% or 30%or so. To prevent suction on the Work the addition of such colloids aspolymerized oils, particularly polymerized tung oil, aluminum tungate orthe aluminum soap of fish oil are serviceable. Rubber also may be usedas a colloiding material. Certain waxes may be used in moderate amount,although not as satisfactory for this specific purpose as the abovementioned colloids. The waxes'as a rule diminish the gloss; aconsideration of The alkali-proof some importance in thecase offinish'fon stucco, which usually is specified as dull or matt.Sapomfiable waxes such as beeswax, which have a slow neutrallzing actionon the free alkali of concrete are not desirable in a priming coat andare not as effective as much as lime is the active ingredient, to a verylarge extent, in concrete, the lime soaps of these oils may beadvantageously used. The aluminum soaps however have pronouncedcolloiding or bodying properties and are to be preferred when a viscousoil is desired.

The oils from which the metallic soap is prepared may be treated so asto, be completely saponified by the use of the requisite amount ofcaustic alkali and subsequent if accompanied by a large proportion ofunsaponifiable material, is not always objectionable.

In Ser. No. 497,934, filed May 24, 1909, I have set forth the advantagesof applying 5 to concrete a priming coat of an oily character containingfatty acids, especially those of siccative oils and have enumerated thefollowing illustrative formulas ;(A) one part of free fatty acid fromlinseed oil, one

part of linseed oil and one part of tung oil;

(B) equal parts of linseed oil and linseed oil fatty acids; (C) equalparts of linseed oil, linseed oil fatty acids and gum thus (D) linseedoil eight parts, linseed oil fatty acids seven parts, tung 011 threeparts, resin two parts, lithopone 15 parts and gypsum four partsotherresins such as Manila or kauri copal being substituted for the resin, ifdesired, or the resinous material omitted entirely, or increased and theoil reduced in amount to make a more rapidly drying composition; linseedoil fatty acids seven parts, kauri copal ten parts, resin three parts,benzin six parts, turpentine three 85 parts and zinc 'sulfid twentyparts.

I have observed that the fatty acid of tung oil possesses the desirablehigh speed of neutralization characteristic of linseed oil fatty acidsand certain others, that like $0 the linseed oil fatty acids the tungacids are miscible with other oils and thinners such as used in varnishmaking, that they have excellent siccative qualities in the presence ofsmall amounts of driers and that they as have a specific waterproofingquality rendering these tung acids very useful in the priming ofconcrete subject to extreme service conditions. Tung acids may thereforebe used in the above formulas A to E inclusive W when conditionsindicate a greater adaptability for the purpose in hand, than the fattyacids of linseed oil.- In the above last mentioned formulas anunsaponifiable or substantially unsaponifiable resin such as Jelutongrubber resin may be substituted for the essentially saponifiable kauri,Manila copal or resin, or for the linseed and Chinese wood oil. Itshould be noted, however, that Chinese wood oil is more resistant 0 tolime 'saponification than linseed oil. Al-

though tung oil is a glycerin and is saponi :fied with considerable easeby potash or soda or other alkali forming a water-soluble soap,

,it does not saponify easily when in contact 05 with the free lime ofcement, provided neither potash or soda are present in more than minuteamounts as is the case with some kinds of Portland cement. Thus tung oilhas certain advantages over linseed oil in this respect. Tung oilbelongs to a class of oils which are rather easily acted on by light toform what appear to be polymerized bodies and in the polymeric orchanged condition are not as sensitive to free lime.

Many drying and non drying oils may be polymerized by heating to a hightempera ture for a short period. Linseed oil polymerizes at temperaturesbetween 250- 300 deg. (1. although at somewhat lower temperatures it ischanged in constitution more or less. Castor oil, which is a non-dryingoil polymerizes at about the same temperature and then becomes solublein mineral oils and petroleum thinners. Wood oil 'polymerizes easily atsomewhat lower temperatures and gelatinizes to form an elastic compoundwhich is scarcely soluble in most solvents. If it is carefully heatedonly to a point where polymerization begins the product will dissolve insome solvents. The presence of resinous bodies retards gelatini'zationand permits of heating the oil to much higher temperatures withoutsolidification resulting. The inner anhydrids of the fatty acids whichpresum ably form on such heating are not-so easily saponified as the rawoil and if combined with pontianak or similar alkali resistant bodyhaving finish-forming properties a concrete oil may be derived whichserves fairly well on concrete low in potash or soda. It should bestated that the glycerin that of the normal oil, which is a point in itsfavor in connection with the preparation of concrete oils, as glycerinis not only a hygroscopic substance but it is a solvent for lime, andlime in'the form of glycerid may easily exhibit a higher concentrationof hydroxyl ions than lime in only aqueous solution. Tung oil is alsopolymerizedor gelatinized by sulfuric acid, and the product obtained byusing acid' only of moderate concentration may be incorporated inconcrete oil compositions. acids may be polymerized by heat or chemicaltreatment. 'Castor oil or its fatty acids may be polymerized withgelatinization by heating with a concentrated solution of zinc chloridor other condensing agent. The reaction is not probably truepolymerization but it affords a means of preparing a colloidalthickening-agent for; certain solutions. When castor oil it treated withstrong sulfuric acid, it doe not gelatinize like tung oil, but formsricinsulfuric acid and other sulfona-ted products. Some of the otheranimal and vegetable oils act similarly, as is well known. 'Thesulfonated oils may be used Similarlyv the tung.

content of gelatinized tung oil is less than higher temperatures.

as the acid component in acid primers for concrete, or Water-insolublesoaps such as the lime or aluminum or zinc compounds may be used ascolloidal thickeners. The sulfonic radical in such oils reduces thetendency of the soaps prepared therefrom to hydrolyze under theprolonged action of water or dampness. Acid neutralizers soluble inorganic solvents may be obtained from naphthalene by chlorinating toform a hydrochlorid of naphthalene chlorid. This and similarhydrochlorids have the advantage of substantial freedom from corrosiveaction and so may replace hydrochloric acid to advantage. Chlorinatednaphthalene or naphthol and other chlorinated aromatic compounds may beused as thickeners. Chlorinated linseed, tung, cotton-seed,'corn andresin oils and the like also in some forms are useful as thickeners. Thechlorinated compounds of these oils formed by the action of sulfurchlorid are very useful bodying or colloiding agents, as are also thevulcanized oils derived by heating the oils with .sulfur. Sulfur chloridwith rape, tung, linseed, candle nut, soy bean, perilla resin, corn,cotton seed, fish,

peanut, olive, castor, palm, lard, tallow and other oils forms more orless oil-soluble products depending upon the amount of sulfur chloridemployed. The fatty acids from these oils react with sulfur chlorid in adlflerent mannerfrom the glycerids themselves, and as a rule are moresoluble in oils and paint thinners. If these oils are mixed with asolution of Pontianak resin or other resin solution, using preferably asolvent unaffected by sulfur chlorid and to this mixture a suitablequantity of sulfur chlorid is added a more satisfactory incorporation issecured than when the oil is separately treated with sulfur chlorid.

The action of the chlorid on the strongly drying oils is so energeticthat diflicultly soluble compounds are produced unlessgreat care 1staken in their preparation and thesemi-drying oils are more easilytreated with sulfur chlorid for the purpose of producing readily solublebut highly colloidal thickening agents. To obtain these desirablethickening agents free from chlorin the oils may be vulcanized withsulfur at 120 deg. C., more or less. In this case also too great anamount of sulfur produces insoluble bodies and ordinarily from 5% to 10%of sulfur is suflicient. The bodying properties of tung oil are improvedby treatment With only 3% of sulfur. Stearic acid does not absorb sulfurat the vulcanizing temperature of melting point of sulfur, or even atsomewhat Qleic acid, on the contrary absorbs some 10% of sulfur at 130deg. C. to 150 deg. C. and this thickened acid may be used as aneutralizer of concrete alkali in' priming compositions. Some of thenitrated oils, as linseed and castor oils, serve as colloidalthickeners.

Among the solvents suitable for the dissolution of J elut'ong resin andthe like, benzol and its homologues, toluol and xylol are as indicatedmost useful. Carbon bisulfid is likewise eflicient. Carbon tetrachloridand a other chlorids of carbon, such as the chlorid of ethylene andethane alford non-inflamma ble solutions. Petroleum benzin, ligroin,kerosene, light kerosene or heavy benzin, anilin, light oils of woodtar, wood and grain alcohol, acetone, oil of acetone and other ketones,ethers and esters may be employed. Spirits of turpentine, woodturpentine, Russian turpentine, pine oil and fir tree oil may also beused. In the case of alcoholic solutionsand the like, nitracellulose orcelluloid or other colloidal thickener soluble in alcoholic menstruumsmay be incorporated to give body. The barium and calcium soaps ofriclnoleic acid are somewhat soluble in alcoholic bodies and these andsimilar materials may likewise be em- Beeswax consists largely ofcerotic acid and myricyl palmitate with 12% to 15% of hydrocarbons ofthe ethylene series. It is slowly saponified by cement-alkali and .isbest used in the form of an oil-soluble metallic soap. Carnauba andshellac wax are difiicultly soluble in the solvents preferably employedin making concrete oil compositions.

Montan wax and montanic acid, spermaceti, paraliin, scale Wax (a softcrude form of parafiin) ozocerlte, or better its refined form ceresin,candelilla wax, palm wax and- Chinese insect wax may be used.

Other materials which may be incorporated for certain applications arethe resin -esters, e. g. Manila, Congo, colophony. The

esters of phenol, cresol, naphthol and glycerin with these resins andtheir condensation products may. be employed. The condensation productsof phenol, cresol, or other phenolic body with formaldehyde, using abasic or acid condensing agent may if not condensed beyond a certainpoint, be used in solution with Pontianak resin or other similarresinous body and the like.

For general purposes where a thickened composition is desired thefollowing illus rative formula. is especially applicable heattreated'Jelutong resin 25 parts, ceres in 3,30

' Ser. No. 552,178.

sistanoe to alkali.

2 parts oil-soluble compound from cottonseed oil and sulfur chlorid 8parts, tung acids 10 parts, Japan drier 1 part, benzol parts and benzin24 parts. Rubber may be substituted for sulfureted cotton-seed oil inthe case ofvery strongly alkalin cements. Tung acids are exceptionallyood solvents of recovered rubber, and in using this relatively cheaprubber material the rubber stock may be separately heated with the tungacids until solution is effected and then mix with the otheringredients.

In the case of structural steel, which as a reinforcing material is tobe embedded in concrete a rather viscous coating is to be preferred.Mixtures of guayule rubber resin and Pontianak resin in naphtha solutioncarrying a filler of dry finely-ground Portland cement are suitable, asset forth in Recovered rubber may be'used in lieu of guayule and as forsuch purposes a light colored oil is not usually required, mixtures ofother materials such as pitches, tars, as candle tar, gilsonite,elaterite, asphalt and the like may be made use of. A certain degree ofplasticity is desired in such compositions, coupled with good re- Thecomposition must bond both with the steel and the concrete. Theincorporation of Portland cement in the concrete oil aids inassimilatingthe coating composition with the concrete. For this purposea formula of the following description may be employed ;-Pontiana'kresin (heat treated) 25 parts, recovered rubber 10 parts, wax 5 parts,candle tar 5 parts, gilsonite 5 parts'and coal tar naphtha parts, towhich mixture is added sufficient dry Portland cement or other filler tomake a heavy bodied coating mixture.

' By finish-forming constituents as used herein I intend to indicatethose materials capable of forming a thin coherent film, includingresinous bodies and siccative oils.

Paraflin oil and other non-volatile petroleum and non-drying oils havenot true finishforming properties although used to adulterate dryingoils and the like. When introduced into linseed or Chinese wood oil forexample paraflin oil retards drying and after or during the process ofdrying the paraffin oil exudes more or less from the siccative oil filmcausing a greasy surface which collects dust and renders the oil coatingor finish of low durability. Hence, although par-v afiin oil isunsaponifiable it is unsuitedfor' incorporation in the compositions ofthe present invention except in very moderate amounts for fluxing orextending purposes. A small amount of petroleum oil sometimes is presentin pontianak, being introduced at the time ofcoagulation or preparationof the raw gum. As petroleumoil reduces the melting point of Pontianakresin and many substantial amount renders the resin soft and sticky, itsuse as an extending material is not recommended.-

The process involved in the present inven. tion comprises theapplication to cement or concrete objects or surfaces a coating orimpregnating layer of the foregoing compositions or kindredcompositions, which application for large work involves coating orimpregnating by applying the material by means of a brush or spraying bythe aid of a suitable spraying device; or a combination of the twomethods, as for example a priming coat with a sprayer and a finishingcoat or coats by the brush. Smaller articles, such as concrete railroadties, fenceposts, concrete shingles, tiles and the like may be dippedinto a tank containing a solution of the waterproofing material, inwhich case a very satisfactory degree of impregnation may be secured.Several coats may be applied in this way if desired. Rough surfaces ofconcrete buildings, such as a rough stucco finish are best treated byspraying, as the forcible impingement of the composition when impelledfrom a sprayer secures a better anchored coating in many cases. Thepresent invention also contemplates especially the process of applyingsolutions of Jelutong or similar resin or wax or waxlike bodies orwax-resins in conjunction with oils and the like to concrete or cementstructures or articles for the purpose of waterproofing these and henceincludes the process of waterproofing concrete which involvessuperficially impregnating'and coating the exposed surface of concrete,to a greater'or less extent, by dipping spraying brush and the like,with a medium comprising an unsaponifiable or alkali-proof or resinousor waxy-resinous body as hereinbefore set forth in conjunction with atempering or colloiding material such as tung oil, fish oil, thewater-insoluble soaps of these and similar oils, rubber, or waxes,balata, petroleum jelly and the like.

1 With a solvent such as benzol a desirable spraying solution may bemade from crude Pontianak rubber resin in the cold as follows ;the whitepowdery resin obtained from acetone or alcohol extraction process, etc.,is dried without melting, preferably, so as to preserve the granular orcomminuted condition. A vacuum drier may be used to advantage for thispurpose. The dry material is then stirred with a quantity of benzolwithout heating, so as to secure practically a saturated solution. Tothree parts of this solution one part of tung oil and part of Japandrier is added, when the composition is ready to be used. Theincorporation of the materials in the cold that is the production of acold-cut solution produces a flatter drying coating than when the,materials are heat-blended. A still flatter effect is derived by theaddition of about 1} part of ceresin treatment at relatively hightemperatures for rather brief periods; but protracted heating at lowertemperatures also yields stable solutions "provided the precautionshereinbefore indicated are carefully observed: hence the presentinvention also embraces the process of treating shaped masses ofhydraulic cement and the like, which comprises treating a substantiallyunsaponifiable resinous-body such a Jelutong rubber resin by heating toa predetermined temperature and 1 adjusting the period of heat treatmentto cause the resin to become capable of forming stable solutions withhydrocarbon oils and the like; in reducing the treated resin to aflowable form by thinning with a reducing medium containing for examplea hydrocarbon solvent, and in applying the resulting solution to thesurface of said masses to superficially impregnate or coat same with a.water-resistant coating; due regard being had for the condition of theconcrete or other surface as to porosity etc. so that .the consistencyof the solution may be adjusted therefor.

In the case of concrete or stone or other building material exposed tothe disintegrating action of molds and the like, the vehicle derived asabove may contain creosote, anthracene oil or other antiseptic material.

What I claim is- 1. The process of waterproofing concrete which consistsin coating and. superficially impregnatingsa'me with a compositionessentially a substantially unsaponifiable resinousbody and Chinese woodoil.

2. The process of waterproofing concrete which comprises coating andsuperficially impregnating samewith a fluent composition comprisingJelutong rubber resin and Chinese wood oil.

3. The process of impregnating concrete,

which comprises applying thereto a composition comprising cold-cutPontianak resin and Chinese wood oil.

4. The process of impregnating concrete which comprises applying theretoa cold out solution of unfused Pontianak resin in a hydrocarbon solventin conjunction with Chinese wood oil. v

. 5. The process oftreating surfaces to protect same which ccomprisesapplying thereto a composition comprising essentially resinousmaterialof a substantially unsaponifiable character and Chinese wood oilin solution in a suitable thinner'in substantially the proportionsdescribed.

' Signed at Montclair, in the county of Essex and State of New Jersey,this 16th day of October, A. D. 1911.

I CARLETON ELLIS. Witnesses:

BIRDELLA M. ELLIS, NATHANIEL L. FOSTER.

